EP0004808A2 - Process for preparing a ceramic body and cathode-solid electrolyte assembly obtained thereby - Google Patents

Process for preparing a ceramic body and cathode-solid electrolyte assembly obtained thereby Download PDF

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Publication number
EP0004808A2
EP0004808A2 EP79400192A EP79400192A EP0004808A2 EP 0004808 A2 EP0004808 A2 EP 0004808A2 EP 79400192 A EP79400192 A EP 79400192A EP 79400192 A EP79400192 A EP 79400192A EP 0004808 A2 EP0004808 A2 EP 0004808A2
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Prior art keywords
ceramic
conductive material
particles
electrically conductive
powder
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German (de)
French (fr)
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EP0004808B1 (en
EP0004808A3 (en
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Bernard Francois
Jean-Claude Viguie
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/002—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/4505—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/5144—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal with a composition mainly composed of one or more of the metals of the iron group
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/53—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone involving the removal of at least part of the materials of the treated article, e.g. etching, drying of hardened concrete
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/88—Metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/91—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics involving the removal of part of the materials of the treated articles, e.g. etching
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features

Definitions

  • the subject of the present invention is a process for preparing a ceramic part comprising on its surface inclusions of electrically conductive material, such a part being usable in particular for constituting the cathode and the solid electrolyte of a cell d electrolysis of high temperature water vapor for the production of hydrogen gas.
  • water vapor is introduced at a temperature of about 760 - 950 ° C into the cathode part of the cell and it is reduced to gaseous hydrogen on the surface of the solid electrolyte when applied across the terminals of the cell a voltage of the order of magnitude of the volt.
  • cathode-solid electrolyte assemblies which consist of a solid electrolyte layer on which a layer of porous cermet is applied, the metal particles of which constitute the cathode of the cell.
  • Processes are also known for manufacturing ceramic parts comprising inclusions of an electrically conductive material shaped in a single operating process, which consequently avoids the appearance of stresses between the solid electrolyte and the conductive material.
  • a layer of mixture of a conductive material, solid electrolyte and a pore-forming agent is distributed over the solid electrolyte.
  • the proportion by volume of the porogen used, here ammonium carbonate, to produce this mixture is in none of the examples cited, less than 50%.
  • the present invention overcomes these drawbacks. It relates to a process for preparing a ceramic part comprising, flush with its surface, inclusions of electrically conductive material. Therefore, it is not necessary to resort to the use of a porogen to create triple points, necessary, as we have seen previously, to the proper functioning of the cathode. Furthermore, the part obtained according to the method of the invention exhibits satisfactory properties of stability and resistance to mechanical stresses, in particular for use as a cathode associated with a solid electrolyte in a water vapor electrolysis cell at high temperature.
  • the method of manufacturing a ceramic part comprising, flush with its surface, inclusions of electrically conductive material, is characterized in that it consists in depositing, on the bottom of a mold, a small amount of particles of said conductive material, to be placed over the ceramic powder, and to compress the assembly formed by said powder and said particles, then to sinter it at a temperature below the melting temperature of said conductive material.
  • the conductive material used consists of nickel particles and the assembly obtained by simultaneous compression of these nickel particles and ceramic powder is sintered at a temperature of 1300 ° C.
  • the method as characterized above advantageously takes advantage of the weakness which, by carrying out the sintering of a blank of the workpiece, has been distributed, at the desired locations, particles of electrically conductive material, it is possible to achieve simultaneously satisfactory densification of the ceramic and stabilization of the particles of electrically conductive material, which are thus firmly fixed to the ceramic in the desired places.
  • the method of the invention is particularly suitable for the production of a solid cathode-electrolyte assembly for a cell for electrolysis of water vapor at high temperature.
  • a ceramic powder capable of constituting a solid electrolyte and by appropriately distributing particles of electrically conductive material in the surface layer of the blank it is possible to obtain directly by sintering a solid electrolyte part comprising on its surface particles of electrically conductive material joined together to form a conductive cathode network.
  • a solid cathode-electrolyte assembly by electrolysis cell of water vapor at high temperature, it is distributed in the surface layer of said blank, particles of said material in a quantity such that one obtains after sintering, a part comprising on its surface inclusions of electrically conductive material joined together so as to form on the surface of said part a conductive network of the electricity.
  • This embodiment of the process of the invention thus makes it possible to directly obtain a solid cathode-electrolyte seems in which the cathode is formed, during sintering, by the union of metallic particles which thus remain firmly fixed in the ceramic constituting the solid electrolyte.
  • the part obtained, after sintering is subjected to a complementary treatment which consists in forming on said part in contact with said inclusions a coating of electrically conductive material according to a determined route.
  • This additional treatment is carried out in particular when the quantity of particles of electrically conductive material distributed over the surface of the part is not sufficient to form, during sintering, metal inclusions joined together in the form of a conductive network.
  • the metal inclusions constitute the fixing points of a thin and flexible conductive deposit which is then deposited on the part according to a determined path in order to form on the latter a cathode network conductive of electricity firmly anchored in the layer. surface of the room.
  • This additional treatment can be carried out for example by depositing over the entire surface of the part. comprising the inclusions a thin layer of electrically conductive material and then removing certain parts of said layer by photoengraving.
  • the particles of electrically conductive material are in the form of beads or fine particles and they preferably have a size between 3 and 30 p.
  • the powder of said ceramic preferably has a particle size close to 0.02 ⁇ m, that is to say a specific surface at least equal to 50 m 2 / g.
  • the ceramic is a ceramic that conducts oxygen ions, preferably consisting of an oxide or a mixture of ionic conductive oxides such as a mixture of zirconium oxide and yttrium oxide.
  • the electrically conductive material consists of a metal, an alloy or a metallic compound capable of temporarily fixing the hydrogen.
  • this material can consist of nickel.
  • This example relates to the preparation of 15 g discs in yttria zirconia comprising on one of their faces nickel inclusions, at a surface density of 10 mg / cm 2 .
  • this nickel powder is dispersed and deposited by decantation on the surface of a steel disc having a thickness of 15 mm and a diameter of 130 mm.
  • the steel disc is placed on the lower piston of a press so that the surface covered with nickel is a few millimeters below the surface of the table and there is above the nickel powder 15g a powder of yttria zirconia (0.09- Y 2 0 3 - 0.91 ZrO 2 , molar concentration) having a specific surface of at least 50m 2 / g and sieved to a particle aggregate size less than or equal to 0.160 mm, by delicately depositing the zirconia powder on the initial nickel deposit.
  • the zirconia powder is carefully leveled, then the powder mixture is compressed under a pressure of 2 t / cm 2 .
  • a compressed disc which constitutes the blank of the part, this disc having on one of its faces a surface layer in which are distributed particles of nickel.
  • This compressed disc is then placed on a flat support in alumina or in molybdenum by covering with a granulated powder or an intermediate disc in magnesia the face of the disc which contains the nickel particles.
  • Sintered discs are thus obtained which can be used as a solid electrolyte associated with a nickel cathode in a high temperature electrolysis cell.
  • a measurement of the surface resistance of the discs shows that the face of the discs which contains the nickel inclusions is conductive. Furthermore, due to the irregularity of the conductive network formed by the nickel inclusions, these discs have a large number of contact points between the nickel and the ceramic, ie a large number of triple points.
  • the intensity which passes through the material is measured as a function of the potential which is applied to it.
  • the slope of the curve obtained gives an approximation of the number of triple points which is all the greater as ⁇ i is higher for a given Ae.
  • the value reported at 1 cm 2 is less than 100 ⁇ .
  • This example concerns the preparation of 15g discs in yttria zirconia comprising on one of their faces 5 mg / cm 2 of nickel inclusions.
  • Example 2 For this preparation, the same procedure is followed as that of Example 1, the only difference being that only 0.3 g of nickel powder is dispersed on the surface of the steel disc.
  • the face of the discs which includes the nickel inclusions is not conductive, that is to say that these inclusions are not joined together to form a conductive network.
  • a conductive network is formed by then depositing under vacuum on the face of the sintered disc comprising the nickel inclusions, a layer of nickel with a thickness of approximately 2 p. Then we eliminate certain parts of this layer to form a conductive network using the photoengraving technique. Thus, a pattern is formed on the nickel layer in the form of a grid with a period of 10 p and this pattern is then revealed by means of ferric chloride.
  • the layer obtained remains linked to the nickel bridges implanted in the ceramic. Because of its thinness, it is flexible and does not impose unbearable mechanical stresses on the electrolyte disc during thermal cycling occurring during use (0 to 850 ° C).
  • the nickel present on the surface of the part forms a porous structure.

Abstract

L'invention a pour objet un procédé de préparation d'une pièce en céramique comportant, affleurant à sa surface, des inclusions de matériau conducteur de l'électricité. Ce procédé consiste à disposer, sur le fond d'un moule, une petite quantité de particules dudit matériau, à disposer par-dessus de la poudre de céramique, et à comprimer l'ensemble formé par ladite poudre et lesdites particules, puis à le fritter à une température inférieure à la température de fusion dudit matériau conducteur. Application à la réalisation d'ensembles cathode-électrolyte solide pour cellule d'électrolyte de la vapeur d'eau à haute température.The invention relates to a method for preparing a ceramic part comprising, flush with its surface, inclusions of electrically conductive material. This process consists in placing, on the bottom of a mold, a small quantity of particles of said material, in placing above the ceramic powder, and in compressing the assembly formed by said powder and said particles, then in sinter at a temperature below the melting temperature of said conductive material. Application to the production of solid cathode-electrolyte assemblies for a high-temperature water vapor electrolyte cell.

Description

La présente invention a pour objet un procédé de préparation d'une pièce en céramique comportant sur sa surface des inclusions de matériau conducteur de l'électricité, une telle pièce étant utilisable notamment pour constituer la cathode et l'électrolyte solide d'une cellule d'électrolyse de la vapeur d'eau à haute température destinée à la production d'hydrogène gazeux.The subject of the present invention is a process for preparing a ceramic part comprising on its surface inclusions of electrically conductive material, such a part being usable in particular for constituting the cathode and the solid electrolyte of a cell d electrolysis of high temperature water vapor for the production of hydrogen gas.

On sait que, compte tenu de l'importance des besoins en hydrogène dans l'industrie chimique, on a développé récemment des techniques de production d'hydrogène par électrolyse de la vapeur d'eau à haute température dans des cellules comprenant un électrolyte solide généralement constitué par une céramique conductrice des ions oxygène, disposé entre deux électrodes qui jouent respectivement le rôle d'anode et de cathode.It is known that, given the importance of hydrogen requirements in the chemical industry, techniques for the production of hydrogen by electrolysis of water vapor at high temperature have recently been developed in cells comprising a solid electrolyte generally consisting of a ceramic conductive of oxygen ions, placed between two electrodes which respectively play the role of anode and cathode.

Dans ces cellules, la vapeur d'eau est introduite à une température d'environ 760 - 950°C dans la partie cathodique de la cellule et elle est réduite en hydrogène gazeux à la surface de l'électrolyte solide quand on applique aux bornes de la cellule une tension de l'ordre de grandeur du volt.In these cells, water vapor is introduced at a temperature of about 760 - 950 ° C into the cathode part of the cell and it is reduced to gaseous hydrogen on the surface of the solid electrolyte when applied across the terminals of the cell a voltage of the order of magnitude of the volt.

On a constaté que dans une cellule de ce type, la production d'hydrogène gazeux dépend en particulier de la structure de la cathode qui doit être poreuse et qu'elle augmente, avec le nombre de points triples c'est-à-dire le nombre de points de contact entre l'électrolyte solide, la cathode et la vapeur d'eau qui circule dans le compartiment cathodique.It has been found that in a cell of this type, the production of hydrogen gas depends in particular on the structure of the cathode which must be porous and that it increases, with the number of triple points, that is to say the number of contact points between the solid electrolyte, the cathode and the water vapor circulating in the cathode compartment.

Pour obtenir cette grande densité de "points triples", on utilise actuellement des ensembles cathode-électrolyte solide constitués par une couche d'électrolyte solide sur laquelle est appliquée une couche de cermet poreux dont les particules de métal constituent la cathode de la cellule.To obtain this high density of "triple points", cathode-solid electrolyte assemblies are currently used which consist of a solid electrolyte layer on which a layer of porous cermet is applied, the metal particles of which constitute the cathode of the cell.

Cependant, de tels ensembles ont l'inconvénient de ne pas posséder des propriétés satisfaisantes de résistance mécanique car ils sont soumis, dans les conditions de fonctionnement de la cellule, à des sollicitations mécaniques dues en particulier à la différence de dilatation entre les deux couches.However, such assemblies have the drawback of not having satisfactory mechanical strength properties because they are subjected, under the operating conditions of the cell, to mechanical stresses due in particular to the difference in expansion between the two layers.

On connaît également des procédés de fabrication de pièces de céramique comportant des inclusions d'un matériau conducteur de l'électricité façonnées en un seul processus opératoire, ce qui évite par conséquent l'apparition de contraintes entre l'électrolyte solide et le matériau conducteur.Processes are also known for manufacturing ceramic parts comprising inclusions of an electrically conductive material shaped in a single operating process, which consequently avoids the appearance of stresses between the solid electrolyte and the conductive material.

On trouvera un exemple d'un tel procédé connu dans le brevet français 1.513.898, pour "Anodes métalliques pour piles à combustibles galvaniques à haute température à électrolyte solide et procédé pour leur fabrication", déposé au nom de "S.A. Brown Boveri et Cie.".One will find an example of such a process known in French patent 1,513,898, for "Metal anodes for galvanic fuel cells at high temperature with solid electrolyte and process for their manufacture", filed in the name of "SA Brown Boveri et Cie . ".

Comme on s'en rend compte, en particulier à la lecture des exemples donnés dans ce brevet, on répartit sur l'électrolyte solide une couche de mélange d'un matériau conducteur, d'électrolyte solide, et d'un porogène. La proportion en volumes du porogène utilisé, ici du carbonate d'ammonium, pour réaliser ce mélange, n'est dans aucun des exemples cités, inférieure à 50 %.As we realize, in particular on reading the examples given in this patent, a layer of mixture of a conductive material, solid electrolyte and a pore-forming agent is distributed over the solid electrolyte. The proportion by volume of the porogen used, here ammonium carbonate, to produce this mixture, is in none of the examples cited, less than 50%.

Plusieurs inconvénients résultent de l'utilisation de ce porogène.Several drawbacks result from the use of this pore former.

D'une part, il constitue une gêne pour la circulation des gaz. Un coefficient de diffusion naît de cette barrière supplémentaire, ce qui limite la densité de courant superficiel.On the one hand, it constitutes a hindrance for the circulation of gases. A diffusion coefficient arises from this additional barrier, which limits the surface current density.

D'autre part, un tel procédé conduit à une température de frittage qui ne saurait être inférieure à 1600°C, ainsi que le précise le brevet français 1.513.898 (page 2, colonne 1. Cette température prohibe, par conséquent, l'emploi d'un métal tel que le nickel, dont la température de fusion est de 1455°C.On the other hand, such a process leads to a sintering temperature which cannot be lower than 1600 ° C., as specified in French patent 1,513,898 (page 2, column 1. This temperature therefore prohibits the use of a metal such as nickel, the melting point of which is 1455 ° C.

La présente invention remédie à ces inconvénients. Elle a pour objet un procédé-de préparation d'une pièce en céramique comportant, affleurant sa surface, des inclusions de matériau conducteur de l'électricité. De ce fait, il n'est pas nécessaire de recourir à l'utilisation d'un porogène pour créer des points triples, nécessaires, comme on l'a vu précédemment, au bon fonctionnement de la cathode. Par ailleurs, la pièce obtenue selon le procédé de l'invention présente des propriétés satisfaisantes de stabilité et de résistance aux sollicitations mécaniques, notamment pour une utilisation comme cathode associée à un électrolyte solide dans une cellule d'électrolyse de la vapeur d'eau à haute température.The present invention overcomes these drawbacks. It relates to a process for preparing a ceramic part comprising, flush with its surface, inclusions of electrically conductive material. Therefore, it is not necessary to resort to the use of a porogen to create triple points, necessary, as we have seen previously, to the proper functioning of the cathode. Furthermore, the part obtained according to the method of the invention exhibits satisfactory properties of stability and resistance to mechanical stresses, in particular for use as a cathode associated with a solid electrolyte in a water vapor electrolysis cell at high temperature.

Le procédé de fabrication d'une pièce en céramique comportant, affleurant à sa surface, des inclusions de matériau conducteur de l'électricité, se caractérise en ce qu'il consiste à déposer, sur le fond d'un moule une petite quantité de particules dudit matériau conducteur, à disposer par-dessus de la poudre de céramique, et à comprimer l'ensemble formé par ladite poudre et lesdites particules, puis à le fritter à une température inférieure à la température de fusion dudit matériau conducteur.The method of manufacturing a ceramic part comprising, flush with its surface, inclusions of electrically conductive material, is characterized in that it consists in depositing, on the bottom of a mold, a small amount of particles of said conductive material, to be placed over the ceramic powder, and to compress the assembly formed by said powder and said particles, then to sinter it at a temperature below the melting temperature of said conductive material.

De préférence, le matériau conducteur utilisé est constitué par des particules de nickel et l'ensemble obtenu par compression simultanée de ces particules de nickel et de poudre de céramique est fritté à une température de 1300°C.Preferably, the conductive material used consists of nickel particles and the assembly obtained by simultaneous compression of these nickel particles and ceramic powder is sintered at a temperature of 1300 ° C.

Le procédé tel que caractérisé ci-dessus tire avantageusement profit du faii u'en réalisant le frittage d'une ébauche de la pièce dani aquelle ont été réparties, aux endroits voulus, des particules de matériau conducteur de l'électricité, on parvient à réaliser simultanément une densification satisfaisante de la céramique et une stabilisation des particules de matériau conducteur de l'électricité, qui sont ainsi solidement fixées à la céramique aux endroits voulus.The method as characterized above advantageously takes advantage of the weakness which, by carrying out the sintering of a blank of the workpiece, has been distributed, at the desired locations, particles of electrically conductive material, it is possible to achieve simultaneously satisfactory densification of the ceramic and stabilization of the particles of electrically conductive material, which are thus firmly fixed to the ceramic in the desired places.

Aussi, le procédé de l'invention est particulièrement adapté à la réalisation d'un ensemble cathode-électrolyte solide pour cellule d'électrolyse de la vapeur d'eau à haute température. En effet, en préparant l'ébauche à partir d'une poudre de céramique susceptible de constituer un électrolyte solide et en répartissant de façon appropriée dans la couche superficielle de l'ébauche des particules de matériau conducteur de l'électricité, on peut obtenir directement par frittage une pièce en électrolyte solide comportant sur sa surface des particules de matériau conducteur de l'électricité réunies entre elles pour former un réseau cathodique conducteur.Also, the method of the invention is particularly suitable for the production of a solid cathode-electrolyte assembly for a cell for electrolysis of water vapor at high temperature. Indeed, by preparing the blank from a ceramic powder capable of constituting a solid electrolyte and by appropriately distributing particles of electrically conductive material in the surface layer of the blank, it is possible to obtain directly by sintering a solid electrolyte part comprising on its surface particles of electrically conductive material joined together to form a conductive cathode network.

Selon un mode de mise en oeuvre du procédé de l'invention, particulièrement avantageux pour la réalisation d'un ensemble cathode-électrolyte solide par cellule d'électrolyse de la vapeur d'eau à haute température, on répartit dans la couche superficielle de ladite ébauche, des particules dudit matériau en quantité telle qu'on obtienne après frittage, une pièce comportant sur sa surface des inclusions de matériau conducteur de l'électricité réunies entre elles de façon à former à la surface de ladite pièce un réseau conducteur de l'électricité.According to an embodiment of the method of the invention, particularly advantageous for the production of a solid cathode-electrolyte assembly by electrolysis cell of water vapor at high temperature, it is distributed in the surface layer of said blank, particles of said material in a quantity such that one obtains after sintering, a part comprising on its surface inclusions of electrically conductive material joined together so as to form on the surface of said part a conductive network of the electricity.

Ce mode de mise en oeuvre du procédé de l'invention permet ainsi d'obtenir directement un semble cathode-électrolyte solide dans lequel la cathode est formée, lors du frittage, par la réunion des particules métalliques qui restent ainsi solidement fixées dans la céramique constituant l'électrolyte solide.This embodiment of the process of the invention thus makes it possible to directly obtain a solid cathode-electrolyte seems in which the cathode is formed, during sintering, by the union of metallic particles which thus remain firmly fixed in the ceramic constituting the solid electrolyte.

Selon un autre mode de mise en oeuvre du procédé de l'invention, on soumet la pièce obtenue, après frittage, à un traitement complémentaire qui consiste à former sur ladite pièce au contact desdites inclusions un revêtement de matériau conducteur de l'électricité selon un tracé déterminé.According to another embodiment of the method of the invention, the part obtained, after sintering, is subjected to a complementary treatment which consists in forming on said part in contact with said inclusions a coating of electrically conductive material according to a determined route.

Ce traitement complémentaire est notamment effectué lorsque la quantité de particules de matériau conducteur de l'électricité répartie à la surface de la pièce n'est pas suffisante pour former lors du frittage des inclusions métalliques réunies entre elles sous la forme d'un réseau conducteur.This additional treatment is carried out in particular when the quantity of particles of electrically conductive material distributed over the surface of the part is not sufficient to form, during sintering, metal inclusions joined together in the form of a conductive network.

Dans ce cas, les inclusions métalliques constituent les points de fixation d'un dépôt conducteur mince et souple qui est déposé ensuite sur la pièce selon un tracé déterminé afin de former sur cette dernière un réseau cathodique conducteur de l'électricité solidement ancré dans la couche superficielle de la pièce.In this case, the metal inclusions constitute the fixing points of a thin and flexible conductive deposit which is then deposited on the part according to a determined path in order to form on the latter a cathode network conductive of electricity firmly anchored in the layer. surface of the room.

Ce traitement complémentaire peut être réalisé par exemple en déposant sur la totalité de la surface de la pièce comportant les inclusions une couche mince de matériau conducteur de l'électricité et en éliminant ensuite certaines parties de ladite couche par photogravure.This additional treatment can be carried out for example by depositing over the entire surface of the part. comprising the inclusions a thin layer of electrically conductive material and then removing certain parts of said layer by photoengraving.

Selon une caractéristique du procédé de l'invention, les particules de matériau conducteur de l'électricité sont sous la forme de billes ou de fines particules et elles ont de préférence une dimension comprise entre 3 et 30 p.According to a characteristic of the process of the invention, the particles of electrically conductive material are in the form of beads or fine particles and they preferably have a size between 3 and 30 p.

Selon une autre caractéristique du procédé de l'invention, la poudre de ladite céramique a de préférence une dimension de particules voisine de 0,02 um, c'est-à-dire une surface spécifique au moins égale à 50 m2/g.According to another characteristic of the process of the invention, the powder of said ceramic preferably has a particle size close to 0.02 μm, that is to say a specific surface at least equal to 50 m 2 / g.

Lorsque le procédé de l'invention est destiné à la réalisation de pièces utilisables comme cathode associée à un électrolyte solide pour cellule d'électrolyse de la vapeur d'eau, la céramique est une céramique conductrice des ions oxygène, constituée de préférence par un oxyde ou un mélange d'oxydes conducteurs ioniques tels qu'un mélange d'oxyde de zirconium et d'oxyde d'yttrium.When the process of the invention is intended for producing parts which can be used as a cathode associated with a solid electrolyte for a water vapor electrolysis cell, the ceramic is a ceramic that conducts oxygen ions, preferably consisting of an oxide or a mixture of ionic conductive oxides such as a mixture of zirconium oxide and yttrium oxide.

Dans ce cas, le matériau conducteur de l'électricité est constitué par un métal, un alliage ou un composé métallique capable de fixer momentanément l'hydrogène. A titre d'exemple, ce matériau peut être constitué par du nickel.In this case, the electrically conductive material consists of a metal, an alloy or a metallic compound capable of temporarily fixing the hydrogen. By way of example, this material can consist of nickel.

L'invention sera mieux comprise à la lecture des- exemples suivants donnés bien entendu à titre illustratif et non limitatif et se référant au dessin annexé qui est une microphotographie d'une pièce obtenue par le procédé de l'invention.The invention will be better understood on reading the following examples given, of course, by way of nonlimiting illustration and referring to the appended drawing which is a photomicrograph of a part obtained by the method of the invention.

EXEMPLE I.EXAMPLE I.

Cet exemple concerne la préparation de disques de 15g en zircone yttriée comportant sur l'une de leurs faces des inclusions de nickel, à une densité superficielle de 10 mg/cm2.This example relates to the preparation of 15 g discs in yttria zirconia comprising on one of their faces nickel inclusions, at a surface density of 10 mg / cm 2 .

On part d'une poudre de nickel tamisée dans l'acétone entre 10 et 30 µ.We start with a nickel powder sieved in acetone between 10 and 30 µ.

On disperse et on dépose par décantation sur la surface d'un disque en acier ayant une épaisseur de 15 mm et un diamètre de 130 mm, 0,6 g environ de cette poudre de nickel.About 0.6 g of this nickel powder is dispersed and deposited by decantation on the surface of a steel disc having a thickness of 15 mm and a diameter of 130 mm.

On dispose le disque en acier sur le piston inférieur d'une presse de façon que la surface recouverte de nickel se situe à quelques millimètres sous la surface de la table et on dispose au-dessus de la poudre de nickel 15g d'une poudre de zircone yttriée (0,09- Y203 - 0,91 ZrO2, concentration molaire) ayant une surface spécifique d'au moins 50m2/g et tamisée à une dimension d'agrégats de particules inférieure ou égale à 0,160 mm, en déposant délicatement la poudre de zircone sur le dépôt initial de nickel.The steel disc is placed on the lower piston of a press so that the surface covered with nickel is a few millimeters below the surface of the table and there is above the nickel powder 15g a powder of yttria zirconia (0.09- Y 2 0 3 - 0.91 ZrO 2 , molar concentration) having a specific surface of at least 50m 2 / g and sieved to a particle aggregate size less than or equal to 0.160 mm, by delicately depositing the zirconia powder on the initial nickel deposit.

A l'aide d'une réglette, on arase avec soin la poudre de zircone, puis on comprime le mélange de poudre sous une pression de 2 t/cm2.Using a slide, the zirconia powder is carefully leveled, then the powder mixture is compressed under a pressure of 2 t / cm 2 .

On obtient ainsi un disque comprimé qui constitue l'ébauche de la pièce, ce disque présentant sur l'une de ses faces une couche superficielle dans laquelle sont réparties des particules de nickel.A compressed disc is thus obtained which constitutes the blank of the part, this disc having on one of its faces a surface layer in which are distributed particles of nickel.

On place ensuite ce disque comprimé sur un support plan en alumine ou en molybdène en recouvrant d'une poudre granulée ou d'un disque intercalaire en magnésie la face du disque qui comporte les particules de nickel.This compressed disc is then placed on a flat support in alumina or in molybdenum by covering with a granulated powder or an intermediate disc in magnesia the face of the disc which contains the nickel particles.

On peut empiler plusieurs disques de cette façon, en disposant ensuite un poids d'environ 500g sur le sommet de l'empilement pour lutter contre des déformations éventuelles au cours du frittage. On réalise ensuite le frittage des disques en plaçant l'empilement de disques disposé sur le support plan dans un four dans lequel circule un courant d'hydrogène gazeux. On porte l'empilement dans le four à une température de 1300°C en le chauffant à une vitesse de 100°C/h et on le maintient à cette température pendant 8 heures environ.Several discs can be stacked in this way, then placing a weight of around 500g on the top of the stack to fight against possible deformations during sintering. Sintering of the discs is then carried out by placing the stack of discs disposed on the flat support in an oven in which a stream of hydrogen gas circulates. The stack is brought into the oven at a temperature of 1300 ° C. by heating it at a speed of 100 ° C./h and is maintained at this temperature for approximately 8 hours.

On obtient ainsi des disques frittés susceptibles d'être utilisés comme électrolyte solide associé à une cathode en nickel dans une cellule d'électrolyse à haute température.Sintered discs are thus obtained which can be used as a solid electrolyte associated with a nickel cathode in a high temperature electrolysis cell.

En se reportant à la figure annexée qui est une microphotographie d'une coupe du disque ainsi obtenu, on voit que les grains de nickel sont implantés à la surface de la pièce.Referring to the appended figure which is a photomicrograph of a section of the disc thus obtained, it can be seen that the nickel grains are implanted on the surface of the part.

Une mesure de la résistance superficielle des disques montre que la face des disques qui comporte les inclusions de nickel est conductrice. Par ailleurs, en raison de l'irrégularité du réseau conducteur formé par les inclusions de nickel, ces disques comportent un grand nombre de points de contact entre le nickel et la céramique, soit un grand nombre de points triples.A measurement of the surface resistance of the discs shows that the face of the discs which contains the nickel inclusions is conductive. Furthermore, due to the irregularity of the conductive network formed by the nickel inclusions, these discs have a large number of contact points between the nickel and the ceramic, ie a large number of triple points.

Ce nombre peut être caractérisé par la pente de la courbe intensité-potentiel pour i = O. Pour obtenir cette courbe on mesure l'intensité qui passe dans le matériau en fonction du potentiel qui lui est appliqué. Au voisinage de i = O, la pente de la courbe obtenue donne une approximation du nombre de points triples qui est d'autant plus grand que Δi est plus élevé pour un Ae donné. Pour des pressions partielles égales d'eau et d'hydrogène, la valeur rapportée à 1 cm2 est inférieure à 100 Ω.This number can be characterized by the slope of the intensity-potential curve for i = O. To obtain this curve, the intensity which passes through the material is measured as a function of the potential which is applied to it. In the vicinity of i = O, the slope of the curve obtained gives an approximation of the number of triple points which is all the greater as Δi is higher for a given Ae. For equal partial pressures of water and hydrogen, the value reported at 1 cm 2 is less than 100 Ω.

EXEMPLE 2.EXAMPLE 2.

Cet exemple concerne la préparation de disques de 15g en zircone yttriée comportant sur l'une de leurs faces 5 mg/cm2 d'inclusions de nickel.This example concerns the preparation of 15g discs in yttria zirconia comprising on one of their faces 5 mg / cm 2 of nickel inclusions.

Pour cette préparation, on suit le même mode opératoire que celui de l'exemple 1, la seule différence étant que l'on disperse sur la surface du disque en acier, seulement 0,3g de poudre de nickel.For this preparation, the same procedure is followed as that of Example 1, the only difference being that only 0.3 g of nickel powder is dispersed on the surface of the steel disc.

Les conditions de pression pour la fabrication de l'ébauche et les conditions de frittage sont identiques à celles de l'exemple 1.The pressure conditions for the production of the blank and the sintering conditions are identical to those of Example 1.

Après frittage, on constate que la face des disques qui comporte les inclusions de nickel n'est pas conductrice, c'est-à-dire que ces inclusions ne sont pas réunies entre elles pour former un réseau conducteur.After sintering, it is found that the face of the discs which includes the nickel inclusions is not conductive, that is to say that these inclusions are not joined together to form a conductive network.

Dans ce cas, on forme un réseau conducteur en déposant ensuite sous vide sur la face du disque fritté comportant les inclusions de nickel, une couche de nickel d'une épaisseur d'environ 2 p. On élimine ensuite certaines parties de cette couche pour former un réseau conducteur en utilisant la technique de photogravure. Ainsi, on forme sur la couche de nickel un dessin ayant la forme d'une grille de période 10 p et on révèle ensuite ce dessin au moyen de chlorure ferrique.In this case, a conductive network is formed by then depositing under vacuum on the face of the sintered disc comprising the nickel inclusions, a layer of nickel with a thickness of approximately 2 p. Then we eliminate certain parts of this layer to form a conductive network using the photoengraving technique. Thus, a pattern is formed on the nickel layer in the form of a grid with a period of 10 p and this pattern is then revealed by means of ferric chloride.

La couche obtenue reste liée aux ponts de nickel implantés dans la céramique. A cause de sa minceur, elle est souple et n'impose pas de contraintes mécaniques insupportables pour le disque d'électrolyte lors des cyclages thermiques intervenant en cours d'utilisation (0 à 850°C).The layer obtained remains linked to the nickel bridges implanted in the ceramic. Because of its thinness, it is flexible and does not impose unbearable mechanical stresses on the electrolyte disc during thermal cycling occurring during use (0 to 850 ° C).

On note que dans ces deux exemples, le nickel présent à la surface de la pièce forme une structure poreuse.Note that in these two examples, the nickel present on the surface of the part forms a porous structure.

Claims (12)

1. Procédé de fabrication d'une pièce en céramique comportant, affleurant à sa surface, des inclusions de matériau conducteur de l'électricité, caractérisé en ce qu'il consiste à disposer, sur le fond d'un moule, une petite quantité de particules dudit matériau, à disposer par dessus de la poudre de céramique et à comprimer l'ensemble formé par ladite poudre et lesdites particules, puis à le fritter à une température inférieure à la température de fusion dudit matériau conducteur.1. A method of manufacturing a ceramic part comprising, flush with its surface, inclusions of electrically conductive material, characterized in that it consists in placing, on the bottom of a mold, a small amount of particles of said material, to be placed on top of the ceramic powder and to compress the assembly formed by said powder and said particles, then to sinter it at a temperature below the melting temperature of said conductive material. 2. Procédé de préparation d'une pièce en céramique selon la revendication 1, caractérisé en ce que le matériau conducteur est constitué par des particules de nickel et en ce que l'ensemble obtenu par compression simultanée de ces particules de nickel et de poudre de céramique, est fritté à une température de 1300°C.2. Method for preparing a ceramic part according to claim 1, characterized in that the conductive material consists of particles of nickel and in that the assembly obtained by simultaneous compression of these particles of nickel and powder of ceramic, is sintered at a temperature of 1300 ° C. 3. Procédé selon l'une quelconque des revendications 1 et 2, caractérisé en ce que l'on répartit dans la couche superficielle de ladite ébauche des particules dudit matériau en quantité telle qu'on obtienne après frittage, une pièce comportant sur sa surface des inclusions de matériau conducteur de l'électricité réunies entre elles de façon à former à la surface de ladite pièce un réseau conducteur de l'électricité.3. Method according to any one of claims 1 and 2, characterized in that one distributes in the surface layer of said blank particles of said material in an amount such that one obtains after sintering, a part comprising on its surface inclusions of electrically conductive material joined together so as to form on the surface of said part an electrically conductive network. 4. Procédé selon l'une quelconque des revendications 1 et 2, caractérisé en ce qu'après frittage, on forme sur ladite pièce au contact desdites inclusions un revêtement de matériau conducteur de l'électricité présentant un tracé déterminé.4. Method according to any one of claims 1 and 2, characterized in that after sintering, is formed on said part in contact with said inclusions a coating of electrically conductive material having a predetermined outline. 5. Procédé selon la revendication 4, caractérisé en ce qu'on forme ledit revêtement présentant un tracé déterminé en déposant sur toute la surface de ladite pièce une couche dudit matériau et en éliminant ensuite certaines parties de ladite couche par photogravure.5. Method according to claim 4, characterized in that said coating having a determined path by depositing over the entire surface of said part a layer of said material and then removing certain parts of said layer by photoengraving. 6. Procédé selon l'une quelconque des revendications 3 à 5, caractérisé en ce que ladite céramique est une céramique conductrice des ions oxygène.6. Method according to any one of claims 3 to 5, characterized in that said ceramic is a ceramic conductive of oxygen ions. 7. Procédé selon la revendication 6, caractérisé en ce que ladite céramique est constituée par un mélange d'oxydes conducteurs ioniques.7. Method according to claim 6, characterized in that said ceramic is constituted by a mixture of ionic conductive oxides. 8. Procédé selon la revendication 7, caractérisé en ce que ladite céramique est un mélange d'oxyde de zirconium et d'oxyde d'yttrium.8. Method according to claim 7, characterized in that said ceramic is a mixture of zirconium oxide and yttrium oxide. 9. Procédé selon la revendication 1, caractérisé en ce que ledit matériau conducteur de l'électricité est un métal, un alliage ou un composé susceptible de fixer momentanément l'hydrogène.9. Method according to claim 1, characterized in that said electrically conductive material is a metal, an alloy or a compound capable of temporarily fixing hydrogen. 10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que les particules dudit matériau conducteur de l'électricité ont une dimension comprise entre 3 et 30 p.10. Method according to any one of claims 1 to 9, characterized in that the particles of said electrically conductive material have a size between 3 and 30 p. 11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que la poudre de ladite céramique a une surface spécifique au moins égale à 50 m2/g.11. Method according to any one of claims 1 to 10, characterized in that the powder of said ceramic has a specific surface at least equal to 50 m 2 / g. 12. Ensemble cathode-électrolyte solide obtenu par mise en oeuvre du procédé selon l'une quelconque des revendications 6 à 9.12. A solid cathode-electrolyte assembly obtained by implementing the method according to any one of claims 6 to 9.
EP79400192A 1978-03-30 1979-03-26 Process for preparing a ceramic body and cathode-solid electrolyte assembly obtained thereby Expired EP0004808B1 (en)

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